KR101934606B1 - Liquid crystal orientation liquid for light orientation processing technique, and liquid crystal orientation film employing same - Google Patents

Abstract

A liquid crystal alignment film capable of suppressing afterimage due to AC driving generated in an IPS driving method or an FFS driving type liquid crystal display device, and a liquid crystal aligning agent for the photo alignment treatment method therefor. Wherein the content of the component (B) is 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (A), the following components (A), (B) and an organic solvent. (A): one or more kinds of polymers in which any reaction of photodegradation, optical dimerization or photoisomerization proceeds by irradiation with polarized radiation, and anisotropy is imparted in the same direction as the polarization direction or in a direction perpendicular to the polarization direction. Component (B): A polymer containing a structure represented by the following formula (1).
[Chemical Formula 1]

(W _1, W ₂ are, each independently, a divalent organic group having an aromatic group having a carbon number of 6 ~ 30, A is a divalent organic group containing an alkylene group of 2 to 20 carbon atoms)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent for use in a photo-alignment treatment method, and a liquid crystal alignment film using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a liquid crystal aligning agent for producing a liquid crystal alignment film, and a liquid crystal alignment film obtained from the liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal aligning agent used for forming a liquid crystal alignment film capable of imparting a liquid crystal aligning ability by irradiation with polarized ultraviolet rays, and a liquid crystal alignment film obtained from such a liquid crystal aligning agent .

In a liquid crystal display element used in a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of liquid crystals is usually formed in the element.

At present, according to the most industrially popular method, this liquid crystal alignment film is formed by laminating the surface of a polyamic acid film formed on an electrode substrate and / or a polyimide film obtained by imidizing the polyamic acid film with a cloth such as cotton, nylon, And rubbing in one direction.

The rubbing treatment of the film surface in the alignment process of the liquid crystal alignment film is an industrially useful method which is simple and excellent in productivity. However, there is a growing demand for high performance, high definition, and large size liquid crystal display elements, and the demand for scratches, oscillations, effects due to mechanical force and static electricity on the surface of the alignment film caused by the rubbing process, Various problems are becoming clear.

As an alternative to the rubbing treatment, there is known a photo alignment method in which a liquid crystal aligning ability is imparted by irradiating polarized radiation. The liquid crystal alignment treatment by the photo alignment method has been proposed using a photo-isomerization reaction, a photo-crosslinking reaction, and a photo-decomposition reaction (see Non-Patent Document 1).

When polyimide is used for a liquid crystal alignment film for optical alignment, its usefulness is expected because it has higher heat resistance than the other. In Patent Document 1, it has been proposed to use a polyimide film having an alicyclic structure such as a cyclobutane ring in the main chain for the photo alignment method.

Such an optical alignment method is attracting attention as a rubbing-less orientation processing method, and can be industrially produced with a simple manufacturing process. In addition, the IPS alignment method and the fringe field switching (FFS) In the liquid crystal display element, the obtained liquid crystal alignment film can improve the contrast and the viewing angle characteristics of the liquid crystal display element compared with the liquid crystal alignment film obtained by the rubbing treatment.

On the other hand, liquid crystal alignment films used in liquid crystal display devices of the IPS driving method and the FFS driving method are required to have excellent liquid crystal alignability and electrical characteristics, It is necessary to suppress afterimage by driving. However, conventionally, the liquid crystal alignment film obtained by the photo alignment method is insufficient in alignment control force of liquid crystal and its stability, and it is difficult to satisfy the above characteristics.

Japanese Patent Application Laid-Open No. 9-297313

 &Quot; Liquid crystal photo alignment layer " Kidowaki, Ichimura functional material Nov. 1997 Vol. 17 No. 11 Pages 13-22

The present invention relates to a liquid crystal alignment film for a photo alignment treatment method capable of suppressing afterimage caused by an AC drive generated in an IPS drive method or an FFS drive type liquid crystal display device and a liquid crystal alignment film for a liquid crystal alignment film And an object of the present invention is to provide an alignment agent.

The inventor of the present invention has conducted intensive studies in order to achieve the above object, and as a result, it has been found that any one of the photodecomposition, optical quantification, and optical isomerization proceeds and the same direction as the polarization direction It has been found that the above objects can be achieved by a polymer having anisotropy in the direction perpendicular to the polarization direction, a polymer having both rigid aromatic groups and flexible alkylene groups, and a liquid crystal aligning agent containing an organic solvent.

Thus, the present invention provides the following.

1. A liquid crystal aligning agent comprising the following components (A), (B) and an organic solvent, wherein the content of the component (B) is 0.1 to 15 parts by mass based on 100 parts by mass of the component (A).

Component (A): One kind or two kinds of compounds which undergo any reaction among light decomposition, optical dimerization or optical isomerization by irradiation with polarized radiation and which are imparted with anisotropy in the same direction as the polarization direction or in a direction perpendicular to the polarization direction Two or more polymers.

Component (B): A polymer containing a structure represented by the following formula (1).

[Chemical Formula 1]

(In the formula (1), W ₁ and W ₂ are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms, and A is a divalent organic group having an alkylene group having 2 to 20 carbon atoms)

2. The liquid crystal aligning agent according to the above 1, wherein the component (A) is one or two or more kinds of polymers which are irradiated with polarized radiation so that the photodegradation reaction proceeds and anisotropy is imparted in the direction perpendicular to the polarization direction.

3. The polyimide precursor according to item 1, wherein the component (A) contains a structural unit represented by the following formula (2) and at least one polymer selected from the group consisting of the imidized polymer of the polyimide precursor Or the liquid crystal aligning agent described in 2 above.

(2)

In the (expression (2), X ₁ is the following formula (X1-1) ~ (and at least one member selected from the group consisting of structures represented by the X1-9), Y ₁ is a divalent organic group and, R ₁ is A hydrogen atom, or an alkyl group having 1 to 4 carbon atoms)

(3)

In formula (X1-1), R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group , The same or different.

4. The polyimide precursor according to claim 1, wherein the component (A) is a polyimide precursor containing the structural unit represented by the formula (2) in an amount of 60 mol% or more based on 1 mol of the total structural units in the component (A) and an imidization polymer of the polyimide precursor Wherein the liquid crystal aligning agent is at least one selected from the group consisting of the above liquid crystal aligning agents.

5. The liquid crystal aligning agent according to the above 3 or 4, wherein in the formula (2), X ₁ is at least one selected from the group consisting of the structure represented by the formula (X1-1).

6. The liquid crystal alignment according to any one of items 3 to 5 above, wherein X ₁ in the formula (2) is at least one selected from the group consisting of the structures represented by the following formulas (X1-10) to (X1-11) My.

[Chemical Formula 4]

7. In the formula (2), Y ₁ A liquid crystal alignment according to the following formula (4) and (5) any one of said at least one 3 to 6 species selected from the group consisting of structure represented by.

[Chemical Formula 5]

(In the formula (5), Z ₁ represents a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms)

8. The liquid crystal aligning agent according to 7 above, wherein Y ₁ in the formula (2) is a structure represented by the formula (4).

9. The polyimide precursor according to any one of items 1 to 8, wherein the component (B) is at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor Lt; / RTI >

[Chemical Formula 6]

(In the formula (3), X ₂ is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bonding hand in an aromatic group, and Y ₂ is a group represented by the following formulas (Y2-1) and (Y2-2) A ₁ and A ₂ each independently represent a hydrogen atom or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent, and R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(7)

In the (Formula (Y2-1), A ₃ is in a divalent organic group having an alkylene group of 2 to 20 carbon atoms in formula (Y2-2), A ₄ is, -O-, -S-, - NR ₁₂ -, an ester bond, amide bond, thioester bond, a urea bond, a carbonate bond, or a carbamate formate a bond, R ₁₂ is a hydrogen atom, a methyl group, or a t- butoxycarbonyl group, a ₅ is a 2 to 20 carbon atoms Lt; / RTI >

Wherein the component (B) is a polyimide precursor containing a structural unit represented by the formula (3) in an amount of 60 mol% or more based on 1 mol of the total structural units in the component (B) and a polyimide precursor Wherein the liquid crystal aligning agent is at least one kind of polymer selected from the group consisting of the liquid crystal aligning agent and the liquid crystal aligning agent.

11. The liquid crystal alignment according to at least one member the 9 or 10 selected from the group consisting of structures represented by the above formula (3) X ₂ is the following formula (X2-1) ~ (X2-3).

[Chemical Formula 8]

12. The liquid crystal alignment is described in X ₂ in the formula (3) in the above 11, wherein the formula (X2-1).

13. The liquid crystal aligning agent according to any one of the above items 9 to 12, wherein Y ₂ in the formula (3) is at least one selected from the group consisting of structures represented by the following formulas (Y2-3) to (Y2-12).

[Chemical Formula 9]

(Formula (Y2-10) and (according to Y2-11), R ₁₃ is may be, each independently, a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, may be the same or different)

14. A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of 1 to 13 above.

15. A liquid crystal alignment film obtained by coating and firing the liquid crystal aligning agent described in any one of 1 to 13 above, and irradiating further polarized radiation.

16. A liquid crystal alignment film obtained by coating and firing the liquid crystal aligning agent according to any one of 1 to 13 above, irradiating with polarized radiation, and then heating at 150 to 250 ° C.

17. A liquid crystal display element comprising the liquid crystal alignment film according to any one of 14 to 16 above.

The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can suppress the afterimage due to the AC drive generated in the IPS drive method or the FFS drive type liquid crystal display device.

Whether or not the problem of the present invention is solved in the liquid crystal alignment film of the present invention is not necessarily clear, but it is considered as follows.

In general, by increasing the anisotropy of the liquid crystal alignment film and / or increasing the interaction between the liquid crystal alignment film and the liquid crystal, it is possible to suppress the afterimage due to the AC drive generated in the IPS drive method or the FFS drive type liquid crystal display device Is known. On the other hand, although the liquid crystal alignment film obtained by the photo alignment method can give sufficient anisotropy, it is difficult to enhance the interaction with the liquid crystal because a specific portion required to react by irradiation is required at least a certain ratio. Specifically, when a structure capable of enhancing the interaction with the liquid crystal is introduced into the polymer, sufficient anisotropy can not be obtained due to the lowered reactivity of the photoreactive site and the lowered density of the photoreactive site.

The present inventors have found that a polymer (B) having a structure similar to a liquid crystal having both a rigid skeleton containing an aromatic group and a flexible skeleton containing an alkylene group is added to the component (A) to which anisotropy is imparted by irradiating with polarized radiation ) Component is preferably mixed with a specific amount of the component (A) to increase the interaction between the liquid crystal alignment film and the liquid crystal alignment film obtained by the photo alignment method while maintaining anisotropy when the polarized radiation is irradiated I found out.

Since the component (B) having a skeleton similar to a liquid crystal has a flexible skeleton, it is expected that the mobility when heated is high. There are several heating processes in the optical alignment treatment and liquid crystal display device production. The inventors of the present invention have considered that during the heating process, the mobility of the component (B) is improved and the polarized radiation is rearranged along the anisotropy imparted by irradiation. It is considered that even when the liquid crystal alignment film obtained by the photo alignment method is used, the liquid crystal alignment film having high anisotropy and high interaction with the liquid crystal can be obtained.

From the above, it can be considered that the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has high liquid crystal alignability and can suppress the afterimage due to the AC drive generated in the IPS drive method or the FFS drive type liquid crystal display device do.

≪ Component (A) >

The component (A) contained in the liquid crystal aligning agent of the present invention can be obtained by irradiating polarized radiation so that any reaction between photodecomposition, optical dimerization or optical isomerization proceeds and the polarizing direction And one or more polymers having anisotropy in the vertical direction.

The structure of the component (A) of the present invention is not particularly limited as long as it is a polymer having a site where any reaction among photo decomposition, optical dimerization, or photo isomerization proceeds by irradiation with radiation. Specifically, as a structure in which the photo-dimerization reaction proceeds, a polymer containing a structure having a cinnamoyl group represented by the following formula (A-1) can be exemplified. As the structure in which the photoisomerization reaction proceeds, a polymer containing an azobenzene skeleton represented by the following formula (A-2) can be mentioned. As the structure in which the photodegradation reaction proceeds, at least one kind of polymer selected from the group consisting of a polymer containing an imide skeleton having an alicyclic group represented by the following formula (A-3) and a precursor of the polymer .

In the formula (A-1), Q is a divalent aromatic group. In the formula (A-3), X is a tetravalent alicyclic group and Y is a divalent organic group.

The liquid crystal alignment film obtained is high in heat resistance, and in the case of a liquid crystal display device, a liquid crystal display device having high reliability of a high voltage holding ratio can be obtained and the obtained liquid crystal alignment film has high anisotropy, More preferred is an imide skeleton having an ester group and an imide skeleton having an ester group.

[Chemical formula 10]

In the formula (A-1), Q is a divalent aromatic group. In the formula (A-3), X is a tetravalent alicyclic group and Y is a divalent organic group.

As the polymer containing an imide structure having an alicyclic skeleton and the precursor of the polymer, since the sensitivity of the photoreaction is high and the anisotropy of the obtained liquid crystal alignment film is high, the component (A) 2) and an imidized polymer of the polyimide precursor are preferable. From the viewpoint of solubility in an organic solvent, a polyimide precursor containing a structural unit represented by the following formula (2) is particularly preferable.

(11)

In formula (2), R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of easiness of imidization by heating, a hydrogen atom or a methyl group is particularly preferable. X ₁ is at least one member selected from the group consisting of the structures represented by the following formulas (X1-1) to (X1-9).

[Chemical Formula 12]

In formula (X1-1), R ₃ , R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group , The same or different. R ₁ , R ₂ , R ₃ and R ₄ are preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom, And at least one member selected from the group consisting of structures represented by formulas (X1-10) to (X1-11).

[Chemical Formula 13]

Y ₁ is a divalent organic group, and its structure is not particularly limited. (4) and (5) because of the high anisotropy of the resulting liquid crystal alignment film.

[Chemical Formula 14]

In the formula (5), Z ₁ is a single bond, an ester bond, an amide bond, a thioester bond or a divalent organic group having 2 to 10 carbon atoms.

In the Z ₁ , the ester bond is represented by -C (O) O- or -OC (O) -. The amide bond may represent a structure represented by -C (O) NH-, or -C (O) NR-, -NHC (O) - or -NRC (O) -. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group. Examples of the alkenyl group include those obtained by substituting one or more CH-CH structures present in the alkyl group with a C = C structure, and more specifically, a vinyl group, allyl group, 1-propenyl group, A phenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group and a cyclohexenyl group. As the alkynyl group, those having at least one CH ₂ -CH ₂ structure present in the above alkyl group substituted with a C≡C structure can be mentioned, and more specifically, an ethynyl group, 1-propynyl group, 2-propynyl group And the like. The aryl group includes, for example, a phenyl group.

The thioester bond may represent a structure represented by -C (O) S-, or -SC (O) -.

When Z ₁ is an organic group having 2 to 10 carbon atoms, it can be represented by the following formula (6).

[Chemical Formula 15]

Z ₄ , Z ₅ and Z ₆ each independently represent a single bond, -O-, -S-, -NR ₁₁ -, an ester bond, an amide bond, a thioester bond, a urea bond, A carbonate bond, or a carbamate bond. R ₁₁ is a hydrogen atom, a methyl group, or a t-butoxycarbonyl group.

Z ₄ , Z ₅ and Z ₆ , the ester bond, amide bond and thioester bond may have the same structures as the above-mentioned ester bond, amide bond and thioester bond.

The urea bond may represent a structure represented by -NH-C (O) NH-, or -NR-C (O) NR-. R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and examples thereof include the same alkyl, alkenyl, alkynyl and aryl groups as mentioned above.

The carbonate bond may represent a structure represented by -O-C (O) -O-.

The carbamate bond includes a structure represented by -NH-C (O) -O-, -OC (O) -NH-, -NR-C (O) -O-, or -OC Lt; / RTI > R is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof having 1 to 10 carbon atoms, and examples thereof include the same alkyl, alkenyl, alkynyl and aryl groups as mentioned above.

R ₉ and R ₁₀ in the formula (6) each independently represent a single bond or a structure selected from alkylene groups, alkenylene groups, alkynylene groups, arylene groups, and combinations thereof having 1 to 10 carbon atoms. For which is a single bond R ₉ and R _10, R ₉ or R ₁₀ is a structure selected from the group which alkylene group, alkenylene group, alkynylene group, arylene group, and combinations thereof having 2 to 10 carbon atoms.

Examples of the alkylene group include a structure in which one hydrogen atom is removed from the alkyl group. Specific examples thereof include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, Propylene group, a 1,2-cyclopentylene group, a 1,2-cyclobutylene group, a 1,3-cyclohexylene group, a 1,2- Butylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group and the like.

Examples of the alkenylene group include a structure in which one hydrogen atom is removed from the alkenyl group. More specifically, examples thereof include a 1,1-ethenylene group, a 1,2-ethenylene group, a 1,2-ethenylene methylene group, a 1-methyl-1,2-ethenylene group, 1-ethylene group, 1,2-ethenylene-1,2-ethylene group, 1,2-ethenylene-1,2-propylene group, 1,2- Butylene group, 2-ethenylene-1,4-butylene group and 1,2-ethenylene-1,2-butylene group.

Examples of the alkynylene group include a structure in which one hydrogen atom is removed from the alkynyl group. Specific examples thereof include an ethynylene group, an ethynylene-1,2-ethylene group, an ethynylene-1,2-propylene group, an ethynylene- -Propylene group, ethynylene-1,4-butylene group, ethynylene-1,2-butylene group and the like.

Examples of the arylene group include a structure in which one hydrogen atom is removed from the aryl group. More specifically, examples thereof include a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group.

Z ₁ is a single bond or a structure represented by the following formulas (A1-1) to (A1-25) because a liquid crystal alignment film having good liquid crystal alignability can be obtained when Y ₁ has a structure with high linearity or a rigid structure Is more preferable.

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

Y ₁ is the more rigid structure, since the liquid crystal alignment excellent liquid crystal alignment film is obtained, Y ₁ is a structure represented by the formula (4) is particularly preferred.

In the imidized polymer of the polyimide precursor and the polyimide precursor containing the structural unit represented by the formula (2), the proportion of the structural unit represented by the formula (2) And preferably 60 mol% to 100 mol%. The higher the ratio of the structural unit represented by the above formula (2) is, the more preferable it is from 80 mol% to 100 mol%, and the more preferable it is from 90 mol% to 100 mol%, because a liquid crystal alignment film having good liquid crystal alignability can be obtained .

The component (A) of the present invention may be a polyimide precursor having a structural unit represented by the following formula (7) and a polyimide precursor thereof in addition to the structural unit represented by the above formula (2).

[Chemical Formula 20]

In the formula (7), R ₁ has the same definition as R ₁ in the formula (2). X ₃ is a tetravalent organic group, and its structure is not particularly limited. Specific examples thereof include structures of the following formulas (X-9) to (X-42). From the viewpoint of the availability of the compound, X may be X-17, X-25, X-26, X-27, X-28, X-32 or X-39. Further, it is preferable to use a tetracarboxylic acid dianhydride having an aromatic ring structure from the viewpoint of obtaining a liquid crystal alignment film which can alleviate the residual charges accumulated by the DC voltage, and X is at least one selected from the group consisting of X-26, X-27 , X-28, X-32, X-35, or X-37 are more preferable.

[Chemical Formula 21]

[Chemical Formula 22]

In the formula (7), Y ₃ is a divalent organic group and its structure is not particularly limited. Specific examples of Y ₃ include the following formulas (Y-1) to (Y-74).

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(Y), Y-21, Y-22, Y (Y), and Y (Y) have a structure other than the formula (4) -28, Y-29, Y-30, Y-72, Y-73 or Y-74.

When the ratio of the structural unit represented by the above formula (7) in the component (A) is high, the liquid crystal alignment property of the liquid crystal alignment film is lowered. Therefore, the proportion of the structural unit represented by the formula (7) Is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

≪ Component (B) >

The component (B) of the present invention is a polymer containing a structure represented by the following formula (1).

(31)

In the formula (1), W ₁ and W ₂ are each independently a divalent organic group having an aromatic group having 6 to 30 carbon atoms and may be the same or different. Examples of the aromatic group contained in W ₁ and W ₂ include benzene, naphthalene, anthracene, biphenyl, and terphenyl. A is a divalent organic group having an alkylene group having 2 to 20 carbon atoms. Examples of the alkylene group having 2 to 20 carbon atoms include a 1,1-ethylene group, a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, A 1,6-hexylene group, a 2,3-butylene group, and a 2,4-pentylene group.

The liquid crystal alignment film having a high liquid crystal alignability can be obtained. Therefore, the component (B) is preferably at least one selected from the group consisting of a polyimide precursor containing the structure represented by the formula (1) and an imidization polymer of the polyimide precursor Of the polymer.

Specifically, it is more preferable to be at least one selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidization polymer of the polyimide precursor.

(32)

In the formula (3), R ₂ has the same definition as R _{1 in} the formula (2), including preferred examples. A ₁ and A ₂ each independently represent a hydrogen atom or an alkyl, alkenyl or alkynyl group having 1 to 10 carbon atoms which may have a substituent, and examples thereof include the same structures as the alkyl, alkenyl and alkynyl groups described above .

The alkyl group, alkenyl group and alkynyl group as described above may have a substituent if the number of carbon atoms is 1 to 10 as a whole, or may form a ring structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of the parent skeleton are bonded to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an oligooxy group, an organotio group, an organosilyl group, an acyl group, an ester group, a thioester group, , An alkenyl group, and an alkynyl group.

Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the aryl group as a substituent, a phenyl group can be mentioned. These aryl groups may be further substituted with other substituents described above.

The olganoxy group as a substituent may represent a structure represented by O-R. These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

As the substituent, the olganothiogue may represent a structure represented by -S-R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group and an octylthio group.

As the substituent, the organosilyl group may represent a structure represented by -Si- (R) ₃ . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the alkylsilyl group include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, tripentylsilyl, trihexylsilyl, pentyldimethylsilyl, hexyldimethylsilyl and the like. .

The acyl group as a substituent may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

The ester group as a substituent may represent a structure represented by -C (O) O-R or -OC (O) -R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.

The thioester group which is a substituent may represent a structure represented by -C (S) O-R or -OC (S) -R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.

The phosphoric acid ester group which is a substituent may represent a structure represented by -OP (O) - (OR) ₂ . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents.

The amide group which is a substituent includes a structure represented by -C (O) NH ₂ , -C (O) NHR, -NHC (O) R, -C (O) N (R) ₂ or -NRC . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents.

Examples of the aryl group as the substituent include the same aryl groups as those described above. These aryl groups may be further substituted with other substituents described above.

Examples of the alkyl group as the substituent include the same alkyl groups mentioned above. These alkyl groups may be further substituted with other substituents described above.

Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.

Examples of the alkynyl group as the substituent include the same alkynyl groups as mentioned above. These alkynyl groups may be further substituted with other substituents described above.

In general, when introducing a bulky structure, there is a possibility that the reactivity of the amino group and the liquid crystal orientation may be lowered. Therefore, as A ₁ and A ₂ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable And a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

X ₂ is a tetravalent organic group having an aromatic group having 6 to 20 carbon atoms and having a bonding hand in an aromatic group. Examples of the aromatic group having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, biphenyl and terphenyl. X ₂ is preferably a tetravalent organic group composed solely of an aromatic group and more preferably a group represented by any one of the following formulas (X2-1) to (X2-3) . ≪ / RTI > Among them, the structure represented by the formula (X2-1) is particularly preferable.

(33)

Y ₂ is at least one kind of divalent organic group selected from the group consisting of the following formulas (Y2-1) to (Y2-2).

(34)

In the formula (Y2-1), A ₃ is a divalent organic group having an alkylene group of 2 to 20 carbon atoms, it does not matter even plurality bring an alkylene group. Examples of the alkylene group having 2 to 20 carbon atoms include a 1,1-ethylene group, a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, A 1,6-hexylene group, a 2,3-butylene group, and a 2,4-pentylene group. From the viewpoint of liquid crystal alignability, A ₃ is preferably a divalent organic group having an alkylene group having 2 to 10 carbon atoms.

In the formula (Y2-2), A ₄ represents a single _{bond, -O-, -S-, -NR 12 -} , an ester bond, amide bond, thioester bond, a urea bond, a carbonate bond, a carbamate bond, or , R ₁₂ is a hydrogen atom, a methyl group, or a t-butoxycarbonyl group, and these may have the same structures as those described above. In terms of liquid crystal alignment, A ₅ is an alkylene group of 2 to 20 carbon atoms, may represent the same structure wherein the alkylene group. From the viewpoint of liquid crystal alignability, A ₄ is preferably a single bond, and A ₅ is preferably an alkylene group having 2 to 6 carbon atoms.

Specific examples of Y < ₂ > that can enhance the interaction with the liquid crystal and improve liquid crystal alignability include the structures represented by the following formulas (Y2-3) to (Y2-12). Among them, a structure represented by the following formula (Y2-3) is particularly preferable.

(35)

In the imidized polymer of the polyimide precursor and the polyimide precursor containing the structural unit represented by the formula (3), the proportion of the structural unit represented by the formula (3) And preferably 60 mol% to 100 mol%. The higher the proportion of the structural unit represented by the above formula (3) is, the better the liquid crystal alignment film having the good liquid crystal alignability is obtained, so that it is more preferably 80 mol% to 100 mol%, still more preferably 90 mol% to 100 mol% .

The component (B) used in the present invention may be a polyimide precursor containing a structural unit represented by the following formula (8) in addition to the structural unit represented by the formula (3) and a polyimide precursor thereof.

(36)

In the formula (8), R _2, A _1, and A ₂ is the same defined, including R _2, A _1, and A ₂ and preferred examples of in the formula (3). X ₄ is a tetravalent organic group having an alicyclic group, and the structure thereof is not particularly limited as long as it is a tetravalent organic group having an alicyclic group. (X-1 to X-9), (X-9) to (X-15), (X-22 to 25) ). Y ₄ is a divalent organic group, and the structure thereof is not particularly limited. Specific examples thereof include the formulas (Y2-3) to (Y2-12), the formulas (4), (5) and (Y-1) to (Y-74).

When the proportion of the structural unit represented by the formula (8) contained in the component (B) is high, the liquid crystal alignability of the liquid crystal alignment film is lowered. Therefore, the proportion of the structural unit represented by the formula (8) Is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

≪ Process for producing polyimide precursor >

The polyamic acid ester used as the polyimide precursor used in the present invention can be synthesized by the following methods (1) to (3).

(1) Synthesis from polyamic acid

The polyamic acid ester can be synthesized by esterifying a polyamic acid obtained from a tetracarboxylic acid dianhydride and a diamine.

Concretely, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 4 hours .

The esterifying agent is preferably one which can be easily removed by purification. Examples of the esterifying agent include N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dineopentylbutyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, , 1-propyl-3-p-tolyltriazine, and 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride. The addition amount of the esterifying agent is preferably 2 to 6 molar equivalents relative to 1 mol of the repeating unit of the polyamic acid.

The solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of the polymer, May be used. The concentration at the time of the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass% from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained.

(2) Synthesis by reaction of tetracarboxylic acid diester dichloride with diamine

Polyamic acid esters can be synthesized from tetracarboxylic acid diester dichloride and diamines.

Specifically, the tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, For 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferred since the reaction proceeds mildly. The addition amount of the base is preferably 2 to 4 times the amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or? -Butyrolactone from the viewpoint of the solubility of the monomer and the polymer, and they may be used alone or in combination of two or more. The concentration of the polymer in the synthesis is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained. In order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, it is preferable that the solvent used for the synthesis of the polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent the ambient air from being mixed in the nitrogen atmosphere.

(3) When polyamic acid is synthesized from tetracarboxylic acid diester and diamine

The polyamic acid ester can be synthesized by polycondensation of a tetracarboxylic acid diester and a diamine.

Specifically, the tetracarboxylic acid diester and the diamine are reacted in the presence of a condensing agent, a base and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C for 30 minutes to 24 hours, For 15 hours.

Examples of the condensing agent include triphenylphosphine, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'- carbonyldiimidazole, dimethoxy- (Benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol- (2,3-dihydro-2-thioxo-3-benzoxazolyl) diphenylphosphonate, etc. can be used. have. The amount of the condensing agent to be added is preferably 2 to 3 times the mole of the tetracarboxylic acid diester.

As the base, tertiary amines such as pyridine and triethylamine can be used. The amount of the base to be added is preferably 2 to 4 times the amount of the diamine component from the viewpoint of easy removal and high molecular weight.

In addition, in the above reaction, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably from 0 to 1.0 times the amount of the diamine component.

Among the methods for synthesizing the above three polyamic acid esters, the synthesis method of the above (1) or (2) is particularly preferable because a high molecular weight polyamic acid ester can be obtained.

The solution of the polyamic acid ester obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, the purified polyamic acid ester powder can be obtained at room temperature or by heating and drying. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<Production method of polyamic acid>

Polyamic acid, which is a polyimide precursor used in the present invention, can be synthesized by the following method.

Specifically, the tetracarboxylic acid dianhydride and the diamine are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C for 30 minutes to 24 hours, preferably 1 to 12 hours Can be synthesized.

The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or? -Butyrolactone from the solubility of the monomer and the polymer, Or more may be mixed and used. The concentration of the polymer is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that the precipitation of the polymer does not occur well and the high molecular weight material is easily obtained.

The polyamic acid thus obtained can be recovered by precipitating a polymer by injecting the reaction solution into a poor solvent while stirring well. Further, the precipitation is repeated several times, washed with a poor solvent, and then dried at room temperature or heated to obtain a purified polyamic acid powder. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

<Production method of polyimide>

The polyimide used in the present invention can be prepared by imidizing a polyimide precursor such as the polyamic acid ester or polyamic acid. In the case of producing a polyimide from a polyamic acid ester, chemical imidization by adding a basic catalyst to the polyamic acid solution obtained by dissolving the polyamic acid ester solution or the polyamic acid ester resin powder in an organic solvent is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not lowered in the process of imidization.

The chemical imidization can be carried out by stirring the polyamic acid ester to be imidized in an organic solvent in the presence of a basic catalyst. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, triethylamine is preferred because it has sufficient basicity to proceed the reaction.

The temperature at which the imidization reaction is carried out may be -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time may be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amic ester group. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time. Since the added catalyst remains in the solution after the imidization reaction, it is preferable to recover the imidized polymer obtained by the means described below and redissolve it with an organic solvent to obtain the liquid crystal aligning agent of the present invention .

When a polyimide is produced from polyamic acid, chemical imidization by adding a catalyst to a solution of the polyamic acid obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride is simple. The chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer is not lowered in the process of imidization.

The chemical imidization can be carried out by stirring the polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferred because it has a basicity suitable for proceeding the reaction. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be given. Among them, acetic anhydride is preferable because the purification after completion of the reaction becomes easy.

The temperature at which the imidization reaction is carried out may be -20 ° C to 140 ° C, preferably 0 ° C to 100 ° C, and the reaction time may be 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 molar times, preferably 2 to 20 molar times, and the amount of the acid anhydride is 1 to 50 molar times, preferably 3 to 30 molar times the amount of the amylic acid. The imidization rate of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature, and reaction time.

Since the added catalyst remains in the solution after the imidization reaction of the polyamic acid ester or the polyamic acid, the imidized polymer thus obtained is recovered by the means described below and redissolved in an organic solvent, It is preferable to use a liquid crystal aligning agent.

The solution of the polyimide obtained as described above can be precipitated by pouring into a poor solvent while stirring well. After several times of precipitation and washing with a poor solvent, the purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.

Examples of the poor solvent include, but are not limited to, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene and benzene.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention has a form of a solution in which components (A) and (B) are dissolved in an organic solvent. The molecular weight of the polymer of the component (A) and the polymer of the component (B) is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

The concentration of the polymer containing the component (A) and the component (B) contained in the liquid crystal aligning agent of the present invention can be appropriately changed according to the setting of the thickness of the coating film to be formed, , It is preferably 1% by mass or more from the viewpoint of solubility, and is preferably 10% by mass or less from the viewpoint of the storage stability of the solution. Particularly preferably 2 to 8% by mass.

The component (A) in the liquid crystal aligning agent of the present invention exhibits high anisotropy when irradiated with polarized radiation and exhibits good liquid crystal alignability when used as a liquid crystal alignment film. Therefore, the component (A) To 10% by mass, preferably 2 to 8% by mass. If the content of the component (B) contained in the liquid crystal aligning agent is too large, anisotropy can not be obtained even when the polarized radiation is irradiated, and the liquid crystal alignability becomes insufficient. If the content is too small, . Therefore, the content of the component (B) is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the component (A).

The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the components (A) and (B) are uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- , N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone,? -Butyrolactone, 1,3-dimethyl- imidazolidinone, N, N-dimethylpropanamide, and the like. These may be used alone or in combination of two or more. The solvent may be mixed with the organic solvent as long as the solvent alone can not uniformly dissolve the polymer component and the polymer does not precipitate.

The liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer, a solvent for improving the film uniformity when the liquid crystal aligning agent is applied to the substrate. Such a solvent generally uses a solvent having a lower surface tension than the organic solvent. Specific examples thereof include ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid, isoamyl acetate, Esters and the like. These solvents may be used in combination of two or more.

In the liquid crystal aligning agent of the present invention, other than the above, it is also possible to change the electrical properties such as the dielectric constant and the conductivity of the polymer and the liquid crystal alignment film other than the polymer of the component (A) and the component (B) A silane coupling agent for improving the adhesion between the liquid crystal alignment film and the substrate, a crosslinkable compound for increasing the hardness and density of the film when the film is used as a liquid crystal alignment film, and further, a polyamic acid An imidization promoter for the purpose of efficiently promoting imidization, and the like may be added.

&Lt; Liquid crystal alignment film &

The liquid crystal alignment film of the present invention can be obtained by applying a liquid crystal aligning agent to a substrate, drying and baking the film, and irradiating the film surface with substantially linearly polarized radiation.

The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency. A glass substrate, a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, It is preferable from the viewpoint of simplification of the process. Further, in a reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used only for a substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case. Examples of the application method of the liquid crystal aligning agent of the present invention include a spin coating method, a printing method, and an ink jet method.

The drying and firing steps after the application of the liquid crystal aligning agent of the present invention can be carried out at arbitrary temperature and time. Usually, it is dried at 50 to 120 ° C for 1 to 10 minutes to sufficiently remove the contained organic solvent, and then baked at 150 to 300 ° C for 5 to 120 minutes. The thickness of the coated film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm.

The liquid crystal aligning agent of the present invention is particularly useful when used in a photo-alignment treatment method.

Specific examples of the photo-alignment treatment method include a method of irradiating the surface of the above-mentioned coating film with polarized radiation in a predetermined direction and, if necessary, further heating treatment at a temperature of 150 to 250 ° C to give a liquid crystal aligning ability . As the wavelength of the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 nm to 400 nm are preferable, and those having a wavelength of 200 nm to 400 nm are particularly preferable. Further, in order to improve the liquid crystal alignment property, the coating film substrate may be irradiated with radiation while heating at 50 to 250 ° C. The irradiation dose of the radiation is preferably in the range of 1 to 10,000 mJ / cm 2, and particularly preferably in the range of 100 to 5,000 mJ / cm 2.

It is preferable to conduct the heat treatment at a temperature of 150 to 250 占 폚 after irradiating the polarized ultraviolet ray in order to induce the redistribution of the component (B), and it is more preferable to perform the heat treatment at a temperature of 200 to 250 占 폚 Do.

<Liquid crystal display element>

The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate on which a liquid crystal alignment film is formed from the liquid crystal aligning agent of the present invention by the above-described technique and subjecting it to alignment treatment and then manufacturing a liquid crystal cell by a known method .

The production method of the liquid crystal cell is not particularly limited. For example, a pair of substrates on which a liquid crystal alignment film is formed is placed with spacers of preferably 1 to 30 μm, more preferably 2 to 10 μm interposed therebetween with the liquid crystal alignment film face inside, A method in which liquid crystal is injected and sealed is generally used. The method of enclosing the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal cell is made in a reduced pressure and a liquid crystal is injected, and a dropping method in which liquid crystal is dropped and then encapsulation is performed.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The abbreviations of the compounds used in the present examples and comparative examples and the measurement methods of the respective properties are as follows.

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

GBL:? -Butyrolactone

AIBN: 2,2'-azobisisobutyronitrile

DA-1: The following formula (DA-1)

DA-2: The following formula (DA-2)

MA1: The following formula (MA-1)

[Viscosity]

In the synthesis examples, the viscosity of the polyamic acid ester and the polyamic acid solution was 1.1 ml of a sample amount, the cone rotor TE-1 (1 ° 34 ', R24), and the amount of water was measured using an E-type viscometer TVE-22H The temperature was measured at 25 캜.

[Molecular Weight]

The molecular weight of the polyamic acid ester is measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) of polyethylene glycol and polyethylene oxide ).

GPC apparatus: manufactured by Shodex Corp. (GPC-101)

Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)

Column temperature: 50 ° C

Eluent: N, N- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran ( THF) 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000 and 30,000) manufactured by Tosoh Corporation and polyethylene glycol (peak top molecular weight (Mp) of about 12,000 and 4,000 , 1,000). In order to avoid overlapping of peaks, two samples of samples mixed with four species of 900,000, 100,000, 12,000 and 1,000 and three samples of 150,000, 30,000 and 4,000 were separately measured.

[AC drive baking of FFS driven liquid crystal cell]

On the glass substrate, an ITO electrode having a thickness of 50 nm in the form of an electrode as the first layer, silicon nitride having a thickness of 500 nm in the form of an insulating film in the second layer, and a comb-shaped ITO electrode ( (Hereinafter referred to as &quot; FFS &quot;) driving electrode having an electrode width of 3 mu m, an electrode pitch of 6 mu m, and an electrode height of 50 nm) The alignment agent was applied. Dried on a hot plate at 80 DEG C for 5 minutes and then fired in a hot air circulating oven at 250 DEG C for 60 minutes to form a coating film having a thickness of 100 nm. Ultraviolet rays of 254 nm were irradiated to the coating film surface through a polarizing plate to obtain a substrate having a liquid crystal alignment film formed thereon. In addition, a coating film was formed on a glass substrate having columnar spacers 4 占 퐉 in height, on which electrodes were not formed as counter substrates, and alignment treatment was carried out.

The two sheets of the above-mentioned substrates were set as a pair, a sealant was printed on the substrate, and another sheet was laminated so that the liquid crystal alignment film surface faced the alignment direction at 0 DEG , And the sealant was cured to prepare empty cells. A liquid crystal MLC-2041 (manufactured by Merck Co.) was injected into this empty cell by a low-pressure injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

The VT characteristic (voltage-transmittance characteristic) of this FFS-driven liquid crystal cell under a temperature of 58 캜 was measured, and then a square wave of ± 4 V / 120 Hz was applied for 4 hours. After 4 hours, turn off the voltage, and then allowed to stand 60 minutes under the temperature of 58 ℃, again yielding a difference between the voltage to be measured is a VT characteristic, a rectangular wave is 50% of the transmittance before and after (ΔV _50).

(Synthesis Example 1)

In a 3000 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2394 g of NMP was added and 196.34 g (1.00 mol) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added. While stirring the slurry of the tetracarboxylic acid dianhydride, 101.11 g (0.935 mol) of p-phenylenediamine was added, and NMP was further added so that the solid content concentration became 8 mass%. The mixture was stirred at room temperature for 24 hours To obtain a solution of polyamic acid (PAA-1). The viscosity of this polyamic acid solution at a temperature of 25 캜 was 115 mPa s.

(Synthesis Example 2)

5.73 g (20.0 mmol) of 1,5-bis (4-aminophenoxy) pentane was added to a 100 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 65.4 g of NMP was added, And dissolved by stirring. While stirring the diamine solution, 4.19 g (19.2 mmol) of pyromellitic dianhydride was added, and NMP was further added so that the solid content concentration became 12 mass%. The mixture was stirred at room temperature for 24 hours to obtain polyamic acid (PAA-2) &Lt; / RTI &gt; The viscosity of the polyamic acid solution at 25 캜 was 520 mPa s.

(Synthesis Example 3)

5.42 g (19.2 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid was taken in a 300 ml four-necked flask equipped with a stirrer, and 100 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (43.98 mmol) of triethylamine and 5.17 g (20.0 mmol) of 1,3-bis (4-aminophenoxy) propane were added and dissolved by stirring. 16.60 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (15 ± 2 wt% hydrate) Further, 13.74 g of NMP was added, and the mixture was reacted for 4 hours under water-cooling.

The obtained polyamic acid ester solution was added to 872 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 290 g of 2-propanol five times, and dried to obtain polyamic acid ester resin powder . The molecular weight of the polyamic acid ester was Mn = 13462 and Mw = 28462.

1.08 g of the obtained polyamide acid ester resin powder was taken in a 50 ml Erlenmeyer flask and 9.78 g of NMP was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamide acid ester solution (PAE-1).

(Synthesis Example 4)

309 g of GBL was added to a 1000 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 67.25 g (30.0 g) of 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride mmol). Next, 487 g of NMP was added. While stirring the slurry of the tetracarboxylic acid dianhydride, 31.14 g (28.80 mmol) of p-phenylenediamine was added, NMP was further added so that the solid content concentration became 10 mass%, and the mixture was stirred at room temperature for 24 hours To obtain a solution of polyamic acid (PAA-3). The viscosity of this polyamic acid solution at a temperature of 25 캜 was 471 mPa s.

(Synthesis Example 5)

6.43 g (59.46 mmol) of p-phenylenediamine and 2.49 g (10.49 mmol) of DA-1 were added to a 300 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 195 g of NMP , And dissolved by stirring. While this solution was stirred, 15.09 g (67.31 mmol) of 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride was added, and further NMP , And the mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-4). The viscosity of this polyamic acid solution at 25 캜 was 230 mPa · s.

(Synthesis Example 6)

11.93 g (39.98 mmol) of DA-2 was added to a 300-ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 162 g of NMP was added and dissolved by stirring. While this solution was stirred, 8.03 g (36.82 mmol) of pyromellitic dianhydride was added and NMP was further added so that the solid concentration became 10% by mass. The mixture was stirred at room temperature for 24 hours to obtain a solution of polyamic acid (PAA-5) Solution. The viscosity of the polyamic acid solution at 25 캜 was 108 mPa s.

(Synthesis Example 7)

5.19 g (18.4 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid was taken in a 300 ml four-necked flask equipped with a stirrer, and 107 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (44.0 mmol) of triethylamine and 6.00 g (19.97 mmol) of 1,6-bis (4-aminophenoxy) hexane were added and dissolved by stirring. While this solution was stirred, 16.88 g of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinate was added, and further 15 g of NMP was added and reacted for 4 hours under water cooling . The obtained polyamic acid ester solution was added to 614 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 307 g of 2-propanol five times, and dried to obtain polyamide acid ester resin powder &Lt; / RTI &gt;

The molecular weight of this polyamic acid ester was Mn = 6286 and Mw = 17648.

2.00 g of the obtained polyamic acid ester resin powder was taken in a 50 ml Erlenmeyer flask and 18.04 g of NMP was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamide acid ester solution (PAE-2).

(Synthesis Example 8)

5.19 g (18.4 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid was taken in a 300 ml four-necked flask equipped with a stirrer, and 109 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (44.0 mmol) of triethylamine and 6.28 g (19.97 mmol) of 1,7-bis (4-aminophenoxy) heptane were added and dissolved by stirring. While stirring this solution, 16.87 g of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinate was added, and further 15 g of NMP was added and reacted for 4 hours under water cooling . The resulting polyamide acid ester solution was added to 629 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 314 g of 2-propanol five times, and dried to obtain polyamide acid ester resin powder &Lt; / RTI &gt;

The molecular weight of this polyamic acid ester was Mn = 5004 and Mw = 17542.

2.00 g of the obtained polyamic acid ester resin powder was added to a 50 ml Erlenmeyer flask and 18.02 g of NMP was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamide acid ester solution (PAE-3).

(Synthesis Example 9)

5.19 g (18.4 mmol) of 2,5-bis (methoxycarbonyl) terephthalic acid was taken in a 300 ml four-necked flask equipped with a stirrer, and 112 g of NMP was added and dissolved by stirring. Subsequently, 4.45 g (44.0 mmol) of triethylamine and 6.56 g (19.97 mmol) of 1,8-bis (4-aminophenoxy) octane were added and dissolved by stirring. While stirring this solution, 16.87 g of (2,3-dihydroxy-2-thioxo-3-benzoxazoyl) phosphinate was added, and further 15 g of NMP was added and reacted for 4 hours under water cooling . The resulting polyamide acid ester solution was added to 642 g of 2-propanol while stirring, and the precipitated precipitate was collected by filtration, washed with 321 g of 2-propanol five times, and dried to obtain polyamide acid ester resin powder &Lt; / RTI &gt;

The molecular weight of this polyamic acid ester was Mn = 6319 and Mw = 17702.

2.00 g of the obtained polyamic acid ester resin powder was taken in a 50 ml Erlenmeyer flask and 18.01 g of NMP was added and dissolved by stirring at room temperature for 24 hours to obtain a polyamide acid ester solution (PAE-4).

(Synthesis Example 10)

12.41 g (35.0 mmol) of MA1 was added to a 300 ml four-necked flask equipped with a stirrer, 111.7 g of NMP was added and dissolved, and the mixture was degassed with a diaphragm pump for 6 minutes. Thereafter, 0.287 g (1.80 mmol) of AIBN was added, and further degassing was performed for 6 minutes. Thereafter, the reaction was carried out at 60 DEG C for 30 hours to obtain a polymer solution (MA-1) of methacrylate. This polymer had a number average molecular weight of 13,000 and a weight average molecular weight of 51,000.

(Example 1)

7.13 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 0.29 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 4.60 g of NMP, Was added thereto, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-1).

(Example 2)

3.95 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 0.19 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 3.88 g of NMP and BCS And 0.02 g of 1-butylimidazole were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-2).

(Example 3)

3.79 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 0.37 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 3.89 g of NMP and 3.99 g of BCS were added to a 20- And 0.02 g of 1-butylimidazole were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-3).

(Example 4)

7.42 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 0.08 g of the polyamic acid ester solution (PAE-1) obtained in Synthesis Example 3, 4.53 g of NMP and 3.03 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A-4).

(Comparative Example 1)

4.16 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 3.82 g of NMP and 2.0 g of BCS were added to a 20 ml sample tube into which a stirrer was placed and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B-1).

(Example 5)

The liquid crystal aligning agent (A-1) obtained in Example 1 was filtered with a filter having a size of 1.0 mu m and then an ITO electrode having a thickness of 50 nm as a first layer and an ITO electrode having a thickness of 500 Nm silicon nitride as the first layer and a comb-like ITO electrode (electrode width: 3 mu m, electrode gap: 6 mu m, electrode height: 50 nm) as the third layer was spin coated . Dried on a hot plate at 80 DEG C for 5 minutes and then fired in a hot air circulating oven at 230 DEG C for 15 minutes to form a coating film having a film thickness of 100 nm. Ultraviolet rays of 254 nm were irradiated with 1500 mJ / cm 2 through this polarizing plate, and further heated in a hot-air circulating oven at 230 캜 for 30 minutes to obtain a substrate on which a liquid crystal alignment film was formed. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and alignment treatment was carried out.

A sealing agent is printed on the substrate and the liquid crystal alignment film faces the other side so that the alignment direction is 0 DEG. After that, the sealing agent is cured to form an empty cell Respectively. A liquid crystal MLC-2041 (manufactured by Merck Co.) was injected into this empty cell by a low-pressure injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell.

As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 1.8 ㎷.

(Example 6)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-2) obtained in Example 2 was used. The AC drive bake property of this FFS-driven liquid crystal cell was evaluated. As a result,? V ₅₀ was 1.3 ㎷.

(Example 7)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-3) obtained in Example 3 was used. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 1.2 ㎷.

(Example 8)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-4) obtained in Example 4 was used. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 1.1 ?.

(Comparative Example 2)

An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 6 except that the liquid crystal aligning agent (B-1) obtained in Comparative Example 1 was used. The AC drive bake property of this FFS-driven liquid crystal cell was evaluated. As a result,? V ₅₀ was 5.0 ㎷.

(Example 9)

16.29 g of the polyamic acid solution (PAA-3) obtained in Synthetic Example 4, 0.45 g of the polyamic acid solution (PAA-2) obtained in Synthetic Example 2, 7.38 g of NMP and 6.05 g of BCS were placed in a 50- and 0.23 g of N-α- (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine as an imidization promoter were added and stirred for 30 minutes by a magnetic stirrer Thereby obtaining a liquid crystal aligning agent (A-5).

(Example 10)

10.79 g of the polyamic acid solution (PAA-3) obtained in Synthetic Example 4, 0.31 g of the polyamic acid solution (PAA-5) obtained in Synthetic Example 6, g of NMP and 6.05 g of BCS were added to a 50 ml sample tube equipped with a stirrer And N-α- (9-fluorenylmethoxycarbonyl) -N-t-butoxycarbonyl-L-histidine as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent A-6).

(Example 11)

10.90 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 5, 0.10 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 5.08 g of NMP and 4.26 g of BCS were placed in a 50- and 0.15 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator were added and stirred with a magnetic stirrer for 30 minutes Thereby obtaining a liquid crystal aligning agent (A-7).

(Example 12)

7.45 g of the polyamic acid solution (PAA-4) obtained in Synthetic Example 5, 0.08 g of the polyamide acid ester solution (PAE-2) obtained in Synthetic Example 7, 4.39 g of NMP, And 0.08 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator were added thereto, and the mixture was stirred in a magnetic stirrer for 30 minutes Followed by stirring to obtain a liquid crystal aligning agent (A-8).

(Example 13)

7.43 g of the polyamic acid solution (PAA-4) obtained in Synthetic Example 5, 0.08 g of the polyamide acid ester solution (PAE-3) obtained in Synthetic Example 8, 4.38 g of NMP and 4.38 g of BCS And 0.08 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator were added thereto, and the mixture was stirred with a magnetic stirrer for 30 minutes Followed by stirring to obtain a liquid crystal aligning agent (A-9).

(Example 14)

7.43 g of the polyamic acid solution (PAA-4) obtained in Synthetic Example 5, 0.08 g of the polyamide acid ester solution (PAE-4) obtained in Synthetic Example 9, 4.35 g of NMP, And 0.08 g of N-α- (9-fluorenylmethoxycarbonyl) -N-τ-t-butoxycarbonyl-L-histidine as an imidization accelerator were added thereto, and the mixture was stirred in a magnetic stirrer for 30 minutes Followed by stirring to obtain a liquid crystal aligning agent (A-10).

(Example 15)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-5) obtained in Example 9 was used to irradiate ultraviolet rays of 254 nm at 500 mJ / cm 2. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 0.8 ㎷.

(Example 16)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-6) obtained in Example 10 was used and 5004 mJ / cm 2 of ultraviolet light of 254 nm was irradiated. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 1.0 ㎷.

(Example 17)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-7) obtained in Example 11 was used to irradiate ultraviolet rays of 254 nm at 500 mJ / cm 2. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 0.8 ㎷.

(Example 18)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5, except that the liquid crystal aligning agent (A-8) obtained in Example 12 was used to irradiate ultraviolet rays of 254 nm at 500 mJ / cm 2. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 0.6 ㎷.

(Example 19)

An FFS-driven liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-9) obtained in Example 13 was used and irradiated with ultraviolet light of 254 nm at 500 mJ / cm 2. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 1.1 ?.

(Example 20)

An FFS-driving liquid crystal cell was fabricated in the same manner as in Example 5 except that the liquid crystal aligning agent (A-10) obtained in Example 14 was used and 5004 mJ / cm 2 of ultraviolet light of 254 nm was irradiated. As a result of evaluating the AC drive bake property of this FFS-driven liquid crystal cell,? V ₅₀ was 1.1 ?.

(Example 21)

12.44 g of the polymer solution (M-1) of methacrylate obtained in Synthesis Example 10, 0.32 g of the polyamic acid solution (A-2) obtained in Synthesis Example 2, 2.08 g of NMP And 6.19 g of BCS were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A-11).

(Example 22)

12.41 g of the methacrylate polymer solution (M-1) obtained in Synthesis Example 10, 0.54 g of the polyamic acid solution (A-2) obtained in Synthesis Example 2, 2.09 g of NMP And 6.20 g of BCS were added and stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent (A-12).

(Comparative Example 3)

12.44 g of the polymer solution (M-1) of the methacrylate polymer obtained in Synthesis Example 10, 2.05 g of NMP and 6.21 g of BCS were added to a 50 ml sample tube equipped with a stirrer and stirred at room temperature for 5 hours, To obtain an aligning agent (B-2).

(Example 23)

Using the liquid crystal aligning agent (A-11) obtained in Example 21, a liquid crystal cell was produced in the following order. The substrate was a glass substrate having a size of 30 mm x 40 mm and a thickness of 0.7 mm and provided with a comb-shaped pixel electrode formed by patterning an ITO film. The pixel electrode has a comb-like shape formed by arranging a plurality of elongated electrode elements bent at a central portion. The width of each electrode element in the short direction is 10 占 퐉, and the interval between the electrode elements is 20 占 퐉. Since the pixel electrode forming each pixel is constituted by arranging a plurality of elongated electrode elements bent at the center portion, the shape of each pixel is not a rectangle shape, It has a shape similar to that of large letters. Each pixel is divided into upper and lower portions with the central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side. When the first area and the second area of each pixel are compared with each other, the electrode elements of the pixel electrodes constituting the first area and the second area are different from each other.

In other words, when the alignment treatment direction of a liquid crystal alignment film to be described later is taken as a reference, the electrode elements of the pixel electrodes are formed so as to form an angle of + 15 ° (clockwise) in the first region of the pixel, And the electrode element is formed so as to form an angle (clockwise direction) of -15 degrees. That is, in the first region and the second region of each pixel, the directions of rotation (inflation / switching) of the liquid crystal caused by the application of the voltage between the pixel electrode and the counter electrode are opposite to each other . The liquid crystal aligning agent (A-11) obtained in Example 21 was spin-coated on the prepared substrate on which the electrode was formed. Subsequently, the substrate was dried with a hot plate at 80 DEG C for 90 seconds, and then fired in a hot air circulating oven at 160 DEG C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

Subsequently, ultraviolet rays of 313 nm were irradiated with 500 mJ / cm 2 through a polarizing plate on the coated film surface, and then heated in a hot air circulating oven at 160 캜 to obtain a substrate having a liquid crystal alignment film formed thereon. A coating film was similarly formed on a glass substrate having a columnar spacer having a height of 4 占 퐉, on which no electrode was formed as a counter substrate, and alignment treatment was carried out. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film of one of the substrates. Subsequently, the other substrate was aligned so that the liquid crystal alignment film surface faced the alignment direction at 0 °, and then the sealant was cured to prepare empty cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into this empty cell by a low pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having a configuration of an IPS (In-Planes Switching) mode liquid crystal display element.

The liquid crystal cell for IPS mode obtained by the above method was provided between two polarizing tubes arranged so that the polarization axis thereof was orthogonal to each other and the backlight was turned on in a voltage unapplied state so that the arrangement angle of the liquid crystal cell Respectively. The rotation angle when the liquid crystal cell was rotated from the angle where the second area of the pixel is darkest to the angle where the first area is darkest is calculated as the initial alignment azimuth angle. Subsequently, in an oven at 60 캜, an AC voltage of 8 V _PP was applied for 168 hours at a frequency of 30 Hz. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for 1 hour. After being left standing, the orientation azimuth was similarly measured, and the difference between the orientation azimuths before and after the AC drive was calculated as the angle DELTA (deg.). The smaller the difference between the orientation orientations before and after the AC drive, the better the AC drive bake characteristic can be judged to be. As a result, the difference in orientation azimuth angle before and after the AC drive was 0.5 deg.

(Example 24)

An IPS driving liquid crystal cell was fabricated in the same manner as in Example 23 except that the liquid crystal aligning agent (A-12) obtained in Example 22 was used. The IPS drive liquid crystal cell was evaluated for the AC drive firing characteristics in the same manner as in Example 23. As a result, the difference in orientation azimuth before and after the AC drive was 0.4 deg.

(Comparative Example 4)

An IPS driving liquid crystal cell was fabricated in the same manner as in Example 23 except that the liquid crystal aligning agent (B-2) obtained in Comparative Example 3 was used. The IPS drive liquid crystal cell was evaluated for the AC drive firing characteristics in the same manner as in Example 23. As a result, the difference in orientation azimuth before and after the AC drive was 1.7 deg.

Industrial availability

The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can reduce the afterimage due to the AC drive generated in the IPS drive method or the FFS drive type liquid crystal display device and the relaxation of the residual charge accumulated by the DC voltage is fast , An IPS driving system having excellent afterimage characteristics, a liquid crystal display element of an FFS driving system, and a liquid crystal alignment film of a liquid crystal television.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2011-171227 filed on August 4, 2011 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims (18)

A liquid crystal aligning agent comprising the following components (A), (B) and an organic solvent, wherein the content of the component (B) is 0.1 to 15 parts by mass based on 100 parts by mass of the component (A).
Component (A): One kind or two kinds of compounds which undergo any reaction among light decomposition, optical dimerization or optical isomerization by irradiation with polarized radiation and which are imparted with anisotropy in the same direction as the polarization direction or in a direction perpendicular to the polarization direction Two or more polymers.
Component (B): at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and an imidized polymer of the polyimide precursor.

(X ₂ is a tetravalent organic group having a bond having an aromatic group having from 6 to 20 carbon atoms, and aromatic groups hand, Y ₂ is at least one selected from the group consisting of the following formula (Y2-1) and (Y2-2) Each of A ₁ and A ₂ is independently a hydrogen atom or an alkyl group, an alkenyl group or an alkynyl group having 1 to 10 carbon atoms which may have a substituent, and R ₂ is a hydrogen atom or a carbon number An alkyl group having 1 to 4 carbon atoms.)

(A ₃ is a divalent organic group having an alkylene group of 2 to 20 carbon atoms.) In formula (Y2-2), A ₄ represents a single bond, -O-, -S-, -NR ₁₂ - , An amide bond, a thioester bond, a urea bond, a carbonate bond or a carbamate bond, R ₁₂ is a hydrogen atom, a methyl group or a t-butoxycarbonyl group, and A ₅ is an alkylene group having 2 to 10 carbon atoms. ) The method according to claim 1,
Wherein the component (A) is one or two or more kinds of polymers in which a photodegradation reaction proceeds by irradiation with polarized radiation and anisotropy is imparted in a direction perpendicular to the polarization direction. The method according to claim 1,
Wherein the component (A) is at least one polymer selected from the group consisting of a polyimide precursor containing a structural unit represented by the following formula (2) and an imidization polymer of the polyimide precursor.

(X ₁ is the following formula (X1-1) ~ (and at least one member selected from the group consisting of structures represented by the X1-9), Y ₁ is a divalent organic group, R ₁ is a hydrogen atom, or a C1 Lt; / RTI &gt; to 4)

(Wherein R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group) The method of claim 3,
(A) is a polyimide precursor containing a structural unit represented by the formula (2) in an amount of 60 mol% or more based on 1 mol of all structural units in the component (A), and a group consisting of an imidation polymer of the polyimide precursor &Lt; / RTI &gt; The method of claim 3,
In the formula (2), X ₁ is the liquid crystal orientation at least one member selected from the group consisting of structures represented by the formula (X1-1). The method of claim 3,
In the formula (2), the liquid crystal orientation at least one member selected from the group consisting of X ₁ structure represented by the following formula (X1-10) and (X1-11).

The method of claim 3,
In the formula (2), the liquid crystal orientation at least one member selected from the group consisting of structures represented by Y ₁ is the following formula (4) and (5).

(Z ₁ is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms) 8. The method of claim 7,
In the above formula (2), Y ₁ is a structure represented by the formula (4). The method according to claim 1,
(B) is a polyimide precursor containing a structural unit represented by the formula (3) in an amount of 60 mol% or more based on 1 mol of all structural units in the component (B) and a group consisting of an imidization polymer of the polyimide precursor Wherein the liquid crystal aligning agent is at least one kind of polymer selected. The method according to claim 1,
The formula (3), the liquid crystal alignment at least one member selected from the group consisting of structures X ₂ are represented by the following formula (X2-1) ~ (X2-3) of.

11. The method of claim 10,
The liquid crystal aligning agent wherein X ₂ in the formula (3) is the formula (X2-1). The method according to claim 1,
The formula (3) Y ₂ is the formula (Y2-3) ~ the liquid crystal orientation at least one member selected from the group consisting of the structures represented by (Y2-12) of.

(Formula (Y2-10) and (according to Y2-11), R ₁₃ is may be, each independently, a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, may be the same or different) A liquid crystal alignment film obtained by applying and firing the liquid crystal aligning agent according to any one of claims 1 to 12. A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of claims 1 to 12 and further irradiating with polarized radiation. A liquid crystal alignment film obtained by applying and baking the liquid crystal aligning agent according to any one of claims 1 to 12, irradiating polarized radiation, and then heating the liquid crystal aligning agent at 150 ° C to 300 ° C. A liquid crystal display element comprising the liquid crystal alignment film according to claim 15. A liquid crystal display element comprising the liquid crystal alignment film according to claim 14. delete